U.S. patent application number 10/028132 was filed with the patent office on 2003-09-18 for method of processing a photographic element containing electron transfer agent releasing couplers.
This patent application is currently assigned to Eastman Kodak Company. Invention is credited to Arcus, Robert A., Gordon, Stuart T., Lunt, Sharon R., Southby, David T..
Application Number | 20030175628 10/028132 |
Document ID | / |
Family ID | 21841759 |
Filed Date | 2003-09-18 |
United States Patent
Application |
20030175628 |
Kind Code |
A1 |
Gordon, Stuart T. ; et
al. |
September 18, 2003 |
Method of processing a photographic element containing electron
transfer agent releasing couplers
Abstract
A method of processing a silver bromoiodide photographic element
comprising contacting the photographic element with a color
developer for less than 120 seconds; wherein the photographic
element comprises a support and more than one dye forming unit, and
wherein the dye forming unit closest to the support contains an
electron transfer agent releasing compound represented by the
formula: CAR--(L).sub.n--ETA wherein: CAR is a carrier moiety which
is capable of releasing --(L)n--ETA on reaction with oxidized
developing agent; L is a divalent linking group, n is 0, 1, or 2;
and ETA is a releasable 1-aryl-3-pyrazolidinone electron transfer
agent having a calculated log partition coefficient (c log P)
greater than or equal to 2.40 bonded to L or CAR through either the
nitrogen atom in the 2-position or the oxygen attached to the
3-position of the pyrazolidinone ring.
Inventors: |
Gordon, Stuart T.;
(Rochester, NY) ; Lunt, Sharon R.; (Webster,
NY) ; Southby, David T.; (Rochester, NY) ;
Arcus, Robert A.; (Penfield, NY) |
Correspondence
Address: |
Paul A. Leipold
Patent Legal Staff
Eastman Kodak Company
343 State Street
Rochester
NY
14650-2201
US
|
Assignee: |
Eastman Kodak Company
|
Family ID: |
21841759 |
Appl. No.: |
10/028132 |
Filed: |
December 20, 2001 |
Current U.S.
Class: |
430/448 ;
430/566; 430/963 |
Current CPC
Class: |
G03C 7/30558 20130101;
G03C 7/407 20130101; G03C 7/3022 20130101; G03C 2200/52 20130101;
G03C 2001/03511 20130101 |
Class at
Publication: |
430/448 ;
430/566; 430/963 |
International
Class: |
G03C 007/407 |
Claims
What is claimed is:
1. A method of processing a silver bromoiodide photographic element
comprising contacting the photographic element with a color
developer for less than 120 seconds; wherein the photographic
element comprises a support and more than one dye forming unit, and
wherein the dye forming unit closest to the support contains an
electron transfer agent releasing compound represented by the
formula:CAR--(L).sub.n--ETAwherein: CAR is a carrier moiety which
is capable of releasing --(L)n--ETA on reaction with oxidized
developing agent; L is a divalent linking group, n is 0, 1, or 2;
and ETA is a releasable 1-aryl-3-pyrazolidinone electron transfer
agent having a calculated log partition coefficient (c log P)
greater than or equal to 2.40 bonded to L or CAR through either the
nitrogen atom in the 2-position or the oxygen attached to the
3-position of the pyrazolidinone ring.
2. The method of claim 1 wherein ETA is represented by Formulas I
or II 25wherein: R.sup.2 and R.sup.3 each independently represents
hydrogen, a substituted or unsubstituted alkyl group having from 1
to 12 carbon atoms, CH.sub.2OR.sup.7 or CH.sub.2OC(O)R.sup.7 where
R.sup.7 is a substituted or unsubstituted alkyl, aryl, or a
heteroatom containing group; R.sup.4 and R.sup.5 each independently
represents hydrogen, a substituted or unsubstituted alkyl group
having from 1 to 8 carbon atoms or a substituted or unsubstituted
aryl group having from 6 to 10 carbon atoms; R.sup.6 is a
substituent; and m is 0 to 5; wherein when m is greater than 1, the
R.sup.6 substituents may form a carbocyclic or heterocyclic
ring.
3. The method of claim 2 wherein R.sup.2 and R.sup.3 are
independently alkyl, CH.sub.2OR.sup.7 or CH.sub.2OC(O)R.sup.7
groups containing 3 to 8 carbon atoms; R.sup.4 and R.sup.5 are
hydrogen, R.sup.6 is independently a halogen, a substituted or
unsubstituted alkyl group having from 1 to 8 carbon atoms, a
substituted or unsubstituted alkoxy group having from 1 to 8 carbon
atoms, an amido, sulfonamido, ester, cyano, sulfone, carbamoyl,
uriedo group, or a heteroatom containing group or ring.
4. The method of claim 2 wherein R.sup.4 and R.sup.5 are hydrogen;
and R.sup.2, R.sup.3, and R.sup.6 are as represented in the
following table:
11TABLE ETA No. R.sup.2 R.sup.3 R.sup.6 1 CH.sub.3 CH.sub.2OC(O)iPr
H 2 CH.sub.3 CH.sub.2OC(O)tBu H 3 CH.sub.3 CH.sub.2OC(O)Et
p--CH.sub.3 4 CH.sub.3 CH.sub.2OC(O)Et 3,4- dimethyl 5 H
CH.sub.2OC.sub.4H.sub.9--n p--OCH.sub.3 6 CH.sub.3
CH.sub.2OC(O)CH.sub.2--O--(CH.sub.2).sub.2S(CH.sub.2).sub.2SMe
H
5. The method of claim 1 wherein CAR is a coupler moiety.
6. The method of claim 5 wherein the coupler moiety is a phenol or
naphthol coupler moiety.
7. The method of claim 1 wherein the electron transfer agent
releasing compound is contained in the emulsion layer at a
concentration from about 6 .mu.mole/m.sup.2 to about 500
.mu.mole/m.sup.2.
8. The method of claim 6 wherein the coupler moiety is represented
by the structures: 26where R.sup.12 and R.sup.13 are independently
a ballast group, a hydrogen, or a substituted or unsubstituted
alkyl or aryl group, R.sup.11 is a halogen atom, an alkyl group
having from 1 to 4 carbon atoms or an alkoxy group having from 1 to
4 carbon atoms, and w is 1 or 2.
9. The method of claim 1 wherein the ETA has a calculated log
partition coefficient (c log P) between and including 2.40 and
3.50.
10. The method of claim 1 wherein the dye forming unit closest to
the support is the red dye forming unit.
11. The method of claim 1 wherein the electron transfer agent
releasing compound is contained in the least light sensitive layer
of the dye forming unit.
12. The method of claim 1 wherein the silver bromoiodide
photographic element is contacted with the color developer for 100
seconds or less.
13. The method of claim 1 wherein the silver bromoiodide
photographic element is contacted with the color developer for 60
seconds or less.
14. A method of processing a silver bromoiodide photographic
element comprising contacting the photographic element with a color
developer for 100 seconds or less; wherein the photographic element
comprises a support and more than one dye forming unit, and wherein
the dye forming unit closest to the support contains an electron
transfer agent releasing compound represented by the
formula:CAR--(L).sub.n--ETAwherein: CAR is a coupler moiety which
is capable of releasing --(L)n--ETA on reaction with oxidized
developing agent; L is a divalent linking group, n is 0, 1, or 2;
and ETA is a releasable 1-aryl-3-pyrazolidinone electron transfer
agent having a calculated log partition coefficient (c log P)
greater than or equal to 2.40 wherein ETA is represented by the
formulas: 27wherein: R.sup.2 and R.sup.3 each independently
represents hydrogen, a substituted or unsubstituted alkyl group
having from 1 to 12 carbon atoms, CH.sub.2OR.sup.7 or
CH.sub.2OC(O)R.sup.7 where R.sup.7 is a substituted or
unsubstituted alkyl, aryl or a heteroatom containing group; R.sup.4
and R.sup.5 each independently represents hydrogen, a substituted
or unsubstituted alkyl group having from 1 to 8 carbon atoms or a
substituted or unsubstituted aryl group having from 6 to 10 carbon
atoms; R.sup.6 is independently a substituent; and m is 0 to 5
wherein when m is greater than 1, the R.sup.6 substituents may form
a carbocyclic or heterocyclic ring.
15. The photographic element of claim 14 wherein R.sup.2 and
R.sup.3 are independently alkyl, CH.sub.2OR.sup.7 or
CH.sub.2OC(O)R.sup.7 groups containing 3 to 8 carbon atoms; R.sup.4
and R.sup.5 are hydrogen; and R.sup.6 is independently a halogen, a
substituted or unsubstituted alkyl group having from 1 to 8 carbon
atoms, a substituted or unsubstituted alkoxy group having from 1 to
8 carbon atoms, an amido, sulfonamido, ester, cyano, sulfone,
carbamoyl, uriedo group, or a heteroatom containing group or
ring.
16. The photographic element of claim 14 wherein R.sup.4 and
R.sup.5 are hydrogen; and R.sup.2, R.sup.3 and R.sup.6 are as
represented in the following Table:
12TABLE ETA No. R.sup.2 R.sup.3 R.sup.6 1 CH.sub.3 CH.sub.2OC(O)iPr
H 2 CH.sub.3 CH.sub.2OC(O)tBu H 3 CH.sub.3 CH.sub.2OC(O)Et
p-CH.sub.3 4 CH.sub.3 CH.sub.2OC(O)Et 3,4-dimethyl 5 H
CH.sub.2OC.sub.4H.sub.9-- n p-OCH.sub.3 6 CH.sub.3
CH.sub.2OC(O)CH.sub.2--O--(CH.sub.2).sub.2- S(CH.sub.2).sub.2SMe
H
17. The method of claim 14 wherein the coupler moiety is a phenol
or naphthol coupler moiety.
18. The photographic element of claim 19 wherein the ETA has a
calculated log partition coefficient (c log P) between and
including 2.40 and 3.50.
19. The method of claim 14 wherein the dye forming unit closest to
the support is the red dye forming unit.
20. The method of claim 14 wherein the electron transfer agent
releasing compound is contained in the least light sensitive layer
of the dye forming unit.
21. The method of claim 14 wherein the silver bromoiodide
photographic element is contacted with the color developer for 60
seconds or less.
22. The method of claim 1 wherein the dye forming unit closest to
the support contains a development inhibitor releasing
compound.
23. The method of claim 14 wherein the dye forming unit closest to
the support contains a development inhibitor releasing compound.
Description
FIELD OF THE INVENTION
[0001] This invention relates to a method of processing a silver
halide photographic element containing a compound that releases an
electron transfer agent (ETARC) capable of selective development
acceleration for improved photographic imaging.
BACKGROUND OF THE INVENTION
[0002] The basic processes for obtaining useful color images from
exposed color photographic silver halide materials include several
steps of photochemical processing such as color development, silver
bleaching, silver halide fixing and water washing or dye image
stabilizing using appropriate photochemical compositions and
automatic processing machines. Photographic color developing
compositions are used to provide the desired dye images early in
the photoprocessing method. Such compositions generally contain
color developing agents, for example, 4-amino-3-methyl-N-(2-methane
sulfonamidoethyl)aniline, as reducing agents to react with suitable
color forming couplers to form the desired dyes
[0003] Traditionally, the color development process has required
one or two days for providing the customer with the desired prints.
In recent years, customers have wanted faster service, and in some
locations known as "mini-labs", it is desired to provide the
customer with the desired prints within an hour. This requires the
photoprocessing methods to be even faster, and reducing the
processing time to within a few minutes is the ultimate desire in
the industry. Much effort has been directed towards co-optimizing
photographic film/paper and processes for very short processing
times of two minutes or less.
[0004] Reduction in processing time of the "display" elements or
color photographic papers has been facilitated by a number of
recent innovations, including the use of predominantly silver
chloride emulsions in the display elements. U.S. Pat. No. 4,892,804
(Vincent et al) describes conventional color developing
compositions for use with high chloride photographic elements that
have found considerable commercial success in the photographic
industry.
[0005] Color negative films, however, generally comprise little or
no silver chloride in their emulsions, and generally have silver
bromide as the predominant silver halide. More typically, the
emulsions are silver bromoiodide emulsions with silver iodide
levels up to several mol percent. Such films require these types of
emulsions because emulsions containing high silver chloride have
not demonstrated sufficient light sensitivity to be used as camera
speed materials although they have the advantage of being rapidly
processed without major changes to the color developer
solution.
[0006] When color negative films are processed using a development
time of less than 120 seconds, non-neutral changes in color balance
result. Specifically, the bottom layer is impacted more than the
top layer so a film that yields balanced contrast between layers in
a standard development cycle will produce unwanted contrast
mismatches when processed through a shortened development time.
[0007] Methods to accelerate development of exposed silver halide
grains, which enable higher photographic response with smaller
silver halide grains and/or lower granularity, have been realized.
For example, U.S. Pat. No. 4,912,025 describes the release of
electron transfer agents (ETAs) for development acceleration
without a concomitant granularity and fog increase. These type of
compounds are commonly referred to as electron transfer agent
releasing couplers or ETARCs. More recently, U.S. Pat. No.
5,605,786 describes a method of imagewise release of an ETA where
an --O--CO--(T).sub.n--(ETA) group is attached at the coupling-off
site of the ETARC. In addition, U.S. Pat. No. 4,859,578 describes
1-aryl-3-pyrazolidinone ETAs in combination with a SMRC. Such
compounds, however, are not record selective so this would not
alleviate the contrast mismatch problem. The use of non-ballasted
ETARCs often result in higher contrast in adjacent layers. A class
of ballasted ETARCs is described in U.S. Pat. Nos. 6,110,657 of
Lunt et al; 6,114,103 of Friday et al; and EP 1 111 458 A1
(published Jun. 27, 2001). None of these disclosures, however,
utilizes electron transfer agents with shortened processing
times.
[0008] U.S. Pat. No. 5,972,584 and U.S. Pat. No. 5,932,399 describe
the use of certain electron transfer agents contained in the
developer solution or coated in the film. U.S. Pat. No. 6,020,112
describes the use of electron transfer agents in shortened
processing times when utilized in high chloride silver halide
emulsions. U.S. Pat. No. 5,830,627 describes the use of a blocked
electron transfer agent and a rapid processing cycle. When
processed through a rapid developer containing a special additive,
the electron transfer agent is released in a non-imagewise fashion
and provides improved developability in the coated layer.
[0009] There is still a need for a method of developing films using
rapid processing which does not result in unwanted contrast
mismatches in the developed film.
SUMMARY OF THE INVENTION
[0010] This invention provides a method of processing a silver
bromoiodide photographic element comprising contacting the
photographic element with a color developer for less than 120
seconds; wherein the photographic element comprises a support and
more than one dye forming unit, and wherein the dye forming unit
closest to the support contains an electron transfer agent
releasing compound represented by the formula:
CAR--(L).sub.n--ETA
[0011] wherein:
[0012] CAR is a carrier moiety which is capable of releasing
--(L)n--ETA on reaction with oxidized developing agent;
[0013] L is a divalent linking group, n is 0, 1 or 2; and
[0014] ETA is a releasable 1-aryl-3-pyrazolidinone electron
transfer agent having a calculated log partition coefficient (c log
P) greater than or equal to 2.40 bonded to L or CAR through either
the nitrogen atom in the 2-position or the oxygen attached to the
3-position of the pyrazolidinone ring.
ADVANTAGEOUS EFFECT OF THE INVENTION
[0015] This invention allows for the design of films that provides
neutral contrast in shortened development times, while still
maintaining good curve shape in standard development cycles. The
specific ballasted ETARCs used in the invention can be selectively
coated in the appropriate record to provide contrast enhancement in
whichever areas of the curve need it. Unlike the prior art, which
involves the release of electron transfer agents in a non-imagewise
manner when used with rapid processing, this invention provides the
imagewise release of electron transfer agents. Such imagewise
release provides benefits in imaging performance. The image-wise
release from an ETARC enables a high concentration of ETA to be
present where development is going on to amplify the signal. Also,
in non-imagewise areas there is little or no release of ETA so that
indiscriminate fog density is not amplified as it would be from the
non-imagewise release disclosed in the prior art. Thus, imagewise
release amplifies the desired signal more effectively and the
undesirable noise less effectively than could be achieved from a
non-imagewise release.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The ETARCs utilized in the photographic elements processed
by the method of the invention are represented by the formula
CAR--(L).sub.n--ETA.
[0017] ETA is a 1-aryl-3-pyrazolidinone derivative having a
calculated log partition coefficient (c log P) greater than 2.40
using MedChem v3.54. (Medicinal Chemistry Project, Pomona College,
Claremont, Calif., 1987). Preferably the c log P is between and
includes 2.40 and 3.50. On reaction with oxidized developing agent
during processing, the CAR moiety releases the --(L).sub.n--ETA
fragment. The ETA is released from --(L).sub.n-- and becomes an
active electron transfer agent capable of accelerating development
under processing conditions used to obtain the desired dye
image.
[0018] The electron transfer agent pyrazolidinones that have been
found to be useful in providing development increases are derived
from compounds generally of the type described in U.S. Pat. Nos.
4,209,580; 4,463,081; 4,471,045; and 4,481,287 and in published
Japanese Patent Application. No. 62-123172. Such compounds comprise
a 3-pyrazolidinone structure having an unsubstituted or a
substituted aryl group in the 1-position. Preferably these
compounds have one or more alkyl groups in the 4- or 5-positions of
the pyrazolidinone ring.
[0019] Preferred electron transfer agents suitable for use in this
invention are represented by structural formulas I and II: 1
[0020] R.sup.2 and R.sup.3 each independently represents hydrogen,
a substituted or unsubstituted alkyl group having from 1 to 12
carbon atoms, CH.sub.2OR.sup.7 or CH.sub.2OC(O)R.sup.7 where
R.sup.7 can be a substituted or unsubstituted alkyl, aryl, or a
heteroatom containing group. When R.sup.2 and R.sup.3 are alkyl,
CH.sub.2OR.sup.7 or CH.sub.2OC(O)R.sup.7 groups, and R.sup.7 is a
substituted or unsubstituted alkyl or aryl group, it is preferred
that R.sup.2 and R.sup.3 comprise from 3 to 8 carbon atoms. When
R.sup.7 is a heteroatom containing group, it is preferred that
R.sup.2 and R.sup.3 comprise from 4 to 12 carbon atoms. R.sup.7 may
contain, for example, a morpholino, imidazole, triazole or
tetrazole group, or a sulfide or ether linkage.
[0021] R.sup.4 and R.sup.5 each independently represent hydrogen, a
substituted or unsubstituted alkyl group having from 1 to 8 carbon
atoms or a substituted or unsubstituted aryl group having from 6 to
10 carbon atoms. Preferably R.sup.4 and R.sup.5 each represent
hydrogen.
[0022] R.sup.6, which may be present in the ortho, meta or para
positions of the aromatic ring, is any substituent which does not
interfere with the required log partition coefficient or the
functionality of the ETARC. In one embodiment R.sup.6 independently
represents hydrogen, halogen, a substituted or unsubstituted alkyl
group having from 1 to 8 carbon atoms, a substituted or
unsubstituted alkoxy group having from 1 to 8 carbon atoms, or an
amido, sulfonamido, ester, cyano, sulfone, carbamoyl, uriedo group,
or a heteroatom-containing group or ring. Preferably R.sup.6 is
hydrogen, halogen, a substituted or unsubstituted alkyl group
having from 1 to 8 carbon atoms or a substituted or unsubstituted
alkoxy group having from 1 to 8 carbon atoms. m is 0 to 5. When m
is greater than 1, the R.sup.6 substituents can be the same or
different or can be taken together to form a carbocycle or
heterocyclic ring; and
[0023] Especially preferred releasable electron transfer agents,
suitable for use in this invention, are presented in Table I with
R.sup.4 and R.sup.5 being hydrogen:
1 TABLE I ETA No. R.sup.2 R.sup.3 R.sup.6 1 CH.sub.3
CH.sub.2OC(O)iPr H 2 CH.sub.3 CH.sub.2OC(O)tBu H 3 CH.sub.3
CH.sub.2OC(O)Et p--CH.sub.3 4 CH.sub.3 CH.sub.2OC(O)Et 3,4-dimethyl
5 H CH.sub.2OC.sub.4H.sub.9--n p--OCH.sub.3 6 CH.sub.3
CH.sub.2OC(O)CH.sub.2--O-- H (CH.sub.2).sub.2S(CH.sub.2).sub.2S-
Me
[0024] The amount of ETARC that can be employed with this invention
can be any concentration that is effective for the intended
purpose. A possible range for the compound to be employed is at a
concentration from 6 .mu.mole/m.sup.2 to 500 .mu.mole/m.sup.2. A
preferred concentration range is 20 .mu.mole/m.sup.2 to 140
.mu.mole/m.sup.2.
[0025] The ETA is attached to the coupler at a position that will
cause the ETA to be inactive until released. The point of
attachment of the ETA to the CAR or to the CAR--(L).sub.n-- linking
is through either the nitrogen atom in the 2-position or the oxygen
attached to the 3-position of the pyrazolidinone ring as shown for
structures I or II. Such attachment inactivates the ETA so that it
is unlikely to cause undesirable reactions during storage of the
photographic material. However, the oxidized developer formed in an
imagewise manner as a consequence of silver halide development
reacts with the CAR moiety to lead to the cleavage of the bond
between the CAR and L. L undergoes further reaction to release the
active ETA moiety.
[0026] The linking group --(L).sub.n-- is employed to provide for
controlled release of the ETA moiety from the coupler moiety so
that the effect of accelerated silver halide development can be
quickly attained. L represents a divalent linking group which is
both a good leaving group and allows release of the ETA without a
long delay. n is 0, 1 or 2. In one embodiment L is not --O--CO--.
Various types of known linking groups can be used. These include
quinone methide linking groups such as are disclosed in U.S. Pat.
No. 4,409,323; pyrazolonemethide linking groups such as are
disclosed in U.S. Pat. No. 4,421,845; and intramolecular
nucleophillic displacement type linking groups such as are
disclosed in U.S. Pat. No. 4,248,962. Examples of CAR--L--ETA
include 2
[0027] wherein each R.sup.8 can independently be hydrogen, a
substituted or unsubstituted alkyl group of 1 to 12 carbon atoms or
a substituted or unsubstituted aryl group of 6 to 10 carbon atoms.
More preferably R.sup.8 is a substituted or unsubstituted alkyl
group of 1 to 4 carbon atoms. R.sup.9 is a substituted or
unsubstituted alkyl group of from 1 to 20 carbon atoms, preferably
of from 1 to 4 carbon atoms, or a substituted or unsubstituted aryl
group of from 6 to 20 carbon atoms, preferably of from 6 to 10
carbon atoms. X is an --NO.sub.2, --CN, sulfone, sulfonamide,
halogen or alkoxycarbonyl group, and p is 0 or 1.
[0028] Y represents the atoms necessary to form is a substituted or
unsubstituted carbocyclic aromatic ring, or a substituted or
unsubstituted heterocyclic aromatic ring. Preferably Y forms a
carbocyclic aromatic ring having 6 to 10 carbon atoms or a
5-membered heterocyclic aromatic ring. Suitable heterocyclic rings
include pyrazoles, imidazoles, triazoles, pyrazolotriazoles, etc.
R.sup.10 is a substituted or unsubstituted alkyl or aryl group. Z
is a carbon or nitrogen atom.
[0029] Particularly suitable linking groups are contained within
the formulas representing CAR--L--ETA below: 3
[0030] wherein Y represents the atoms necessary to form a
substituted or unsubstituted phenyl ring, Z is a carbon atom, and
R.sup.9 and p are as defined above. Typical useful linking groups
include: 4
[0031] where R.sup.9 is as defined above and p is 0 or 1.
[0032] CAR is a carrier moiety that is capable of releasing
--(L).sub.n--ETA on reaction with oxidized developing agent. In a
preferred embodiment, CAR is a coupler moiety that can release
--(L).sub.n--ETA from the coupling site during reaction with
oxidized primary amine color developing agent. CAR carriers that
are triggered by reaction with oxidized developing agent are
capable of releasing a photographically useful group (PUG) and are
particularly well known in development inhibitor release (DIR)
technology where the PUG is a development inhibitor. Typical
references to hydroquinone type carriers are U.S. Pat. Nos.
3,379,529; 3,297,445; and 3,975,395. U.S. Pat. No. 4,108,663
discloses similar release from aminophenol and aminonaphthol
carriers, while U.S. Pat. No. 4,684,604 features PUG-releasing
hydrazide carriers. All of these may be classified as
redox-activated carriers for PUG release.
[0033] A far greater body of knowledge has been built up over the
years on carriers in which a coupler releases a PUG upon
condensation with an oxidized primary amine color developing agent.
These can be classified as coupling-activated carriers.
Representative are U.S. Pat. Nos. 3,148,062; 3,227,554; 3,617,291;
3,265,506; 3,632,345; and 3,660,095.
[0034] The coupler, from which the electron transfer agent
pyrazolidinine moiety is released, includes couplers employed in
conventional color-forming photographic processes that yield
colored products based on reactions of couplers with oxidized color
developing agents. The couplers can also yield colorless products
on reaction with oxidized color developing agents. The couplers can
also form dyes that are unstable and which decompose into colorless
products. Further, the couplers can provide dyes that wash out of
the photographic recording materials during processing. Such
couplers are well known to those skilled in the art.
[0035] The coupler can be unballasted or ballasted with an
oil-soluble or fat-tail group. It can be monomeric, or it can form
part of a dimeric, oligomeric, or polymeric coupler in which case
more than one ETA moiety or --(L).sub.n--ETA moiety can be
contained in the ETA releasing compound.
[0036] Many coupler kinds are known. The dyes formed therefrom
generally have their main absorption in the red, green, or blue
regions of the visible spectrum. For example, couplers which form
cyan dyes upon reaction with oxidized color developing agents are
described in such representative patents and publications as: U.S.
Pat. Nos. 2,772,162; 2,895,826; 3,002,836; 3,034,892; 2,474,293;
2,423,730; 2,367,531; 3,041,236; and 4,333,999; and "Farbkuppler:
Eine Literaturubersicht," published in Agfa Mitteilungen, Band III,
pp. 156-175 (1961). In the coupler structures shown below, the
unsatisfied bond indicates the coupling position to which
--(L).sub.n--ETA may be attached.
[0037] Preferably such couplers are phenols and naphthols that give
cyan dyes on reaction with oxidized color developing agent at the
coupling position, i.e., the carbon atom in the 4-position of the
phenol or naphthol. Structures of such preferred cyan couplers are:
5
[0038] where R.sup.12 and R.sup.13 are a ballast group, a hydrogen,
or a substituted or unsubstituted alkyl or aryl group, R.sup.11 is
a halogen atom, an alkyl group having from 1 to 4 carbon atoms or
an alkoxy group having from 1 to 4 carbon atoms, and w is 1 or 2.
Generally R.sup.12 and R.sup.13 are groups having less than 20
carbon atoms.
[0039] Couplers that form magenta dyes upon reaction with oxidized
developing agent are described in such representative patents and
publications as: U.S. Pat. Nos. 2,600,788; 2,369,489; 2,343,703;
2,311,082; 3,824,250; 3,615,502; 4,076,533; 3,152,896; 3,519,429;
3,062,653; 2,908,573; 4,540,654; and "Farbkuppler: Eine
Literaturubersicht," published in Agfa Mitteilungen, Band III, pp.
126-156 (1961).
[0040] Preferably, such couplers are pyrazolones and
pyrazolotriazoles that form magenta dyes upon reaction with
oxidized developing agents at the coupling position, i.e., the
carbon atom in the 4-position for pyrazolones and the 7-position
for pyrazolotriazoles. Structures of such preferred magenta coupler
moieties are: 6
[0041] wherein R.sup.12 and R.sup.13 are defined above. R.sup.13
for pyrazolone structures is typically a phenyl group or a
substituted or unsubstituted phenyl group, such as, for example,
2,4,6-trihalophenyl. For the pyrazolotrazole structures R.sup.13 is
typically alkyl or aryl.
[0042] Couplers that form yellow dyes on reaction with oxidized
color developing agent are described in such representative patents
and publications as U.S. Pat. Nos. 2,875,057; 2,407,210; 3,265,506;
2,298,443; 3,048,194; and 3,447,928; and "Farbkuppler: Eine
Literaturubersicht," published in Agfa Mitteilungen, Band III, pp.
112-126 (1961.
[0043] Preferably, such yellow dye-forming couplers are
acylacetamides, such as benzoylacetanilides and
pivalylacetanilides. These couplers react with oxidized developing
agent at the coupling position, i.e., the active methylene carbon
atom. Structures of such preferred yellow couplers are: 7
[0044] where R.sup.12 and R.sup.13 are defined above and can also
be alkoxy, alkoxycarbonyl, alkanesulfonyl, arenesulfonyl,
aryloxycarbonyl, carbonamido, carbamoyl, sulfonamido, or sulfamoyl.
R.sup.11 is hydrogen or one or more halogen, lower alkyl, (i.e.,
methyl, ethyl), lower alkoxy (i.e., methoxy, ethoxy), or a ballast
(i.e., alkoxy of 16 to 20 carbon atoms) group.
[0045] Couplers that form colorless products upon reaction with
oxidized color developing agent are described in such
representative patents as: U.K. Patent No. 861,138 and U.S. Pat.
Nos. 3,632,345; 3,928,041; 3,958,993; and 3,961,959. Preferably,
such couplers are cyclic carbonyl containing compounds that form
colorless products on reaction with oxidized color developing agent
and have the L group attached to the carbon atom in the
.alpha.-position with respect to the carbonyl group. Structures of
such preferred couplers are: 8
[0046] where R.sup.12 is defined as above, and r is 1 or 2.
[0047] It will be appreciated, depending on the particular coupler
moiety, or the particular developing agent, or the type of
processing, the reaction product of the coupler and oxidized color
developing agent can be: (1) colored and non-diffusible, in which
case it may not be removed during processing from the location
where it is formed; (2) colored and diffusible, in which case it
may be removed during processing from the location where it is
formed or allowed to migrate to a different location; or (3)
colorless and diffusible or non-diffusible, in which case it will
not contribute to image density.
[0048] Especially preferred structures for CAR--(L).sub.n--ETA are
compounds E-1 through E-12, E-15, and E-17. Compounds C-1, C-2, and
C-3 are comparative compounds. 910111213
[0049] Electron transfer agent releasing coupler compounds used in
this invention can be prepared by several synthetic routes. Many of
the preferred ETAs of this patent are esters of
4-(hydroxymethyl)-4-methyl-1-- phenyl-3-pyrazolidinone. Selective
formation of esters at the 4-hydroxymethyl group of
4-(hydroxymethyl)-4-methyl-1-phenyl-3-pyrazolidi- none has been
reported in U.K. Patent 2,073,734 and can be accomplished by
treating 4-(hydroxymethyl)-4-methyl-1-phenyl-3-pyrazolidinone with
an acid chloride in refluxing toluene. The resulting ETA can be
converted, by treatment with phosgene, to the corresponding
carbamoyl chloride that is then caused to react with an amino group
or linking group attached to a coupler. Examples of the synthesis
of these compounds can be found in U.S. Pat. Nos. 6,110,657 of Lunt
et al; 6,114,103 of Friday et al; and EP 1 111 458 A1 (published
Jun. 27, 2001) which are incorporated herein by reference.
[0050] Unless otherwise specifically stated, substituent groups
which may be substituted on molecules herein include any groups,
whether substituted or unsubstituted, which do not destroy
properties necessary for photographic utility. When the term
"group" is applied to the identification of a substituent
containing a substitutable hydrogen, it is intended to encompass
not only the substituent's unsubstituted form, but also its form
further substituted with any group or groups as herein mentioned.
Suitably, the group may be halogen or may be bonded to the
remainder of the molecule by an atom of carbon, silicon, oxygen,
nitrogen, phosphorous, or sulfur. The substituent may be, for
example, halogen, such as chlorine, bromine or fluorine; nitro;
hydroxyl; cyano; carboxyl; or groups which may be further
substituted, such as alkyl, including straight or branched chain
alkyl, such as methyl, trifluoromethyl, ethyl, t-butyl,
3-(2,4-di-t-pentylphenoxy) propyl, and tetradecyl; alkenyl, such as
ethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy,
butoxy, 2-methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy,
tetradecyloxy, 2-(2,4-di-t-pentylphenoxy)ethoxy, and
2-dodecyloxyethoxy; aryl such as phenyl, 4-t-butylphenyl,
2,4,6-trimethylphenyl, naphthyl; aryloxy, such as phenoxy,
2-methylphenoxy, alpha- or beta-naphthyloxy, and 4-tolyloxy;
carbonamido, such as acetamido, benzamido, butyramido,
tetradecanamido, alpha-(2,4-di-t-pentyl-phenoxy)acetamido,
alpha-(2,4-di-t-pentylphenoxy)b- utyramido,
alpha-(3-pentadecylphenoxy)-hexanamido, alpha-(4-hydroxy-3-t-bu-
tylphenoxy)-tetradecanamido, 2-oxo-pyrrolidin-1-yl,
2-oxo-5-tetradecylpyrrolin-1-yl, N-methyltetradecanamido,
N-succinimido, N-phthalimido, 2,5-dioxo-1-oxazolidinyl,
3-dodecyl-2,5-dioxo-1-imidazolyl- , and N-acetyl-N-dodecylaamino,
ethoxycarbonylamino, phenoxycarbonylamino, benzyloxycarbonylamino,
hexadecyloxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino,
phenylcarbonylamino, 2,5-(di-t-pentylphenyl)carbonylamino,
p-dodecyl-phenylcarbonylamino, p-toluylcarbonylamino,
N-methylureido, N,N-dimethylureido, N-methyl-N-dodecylureido,
N-hexadecylureido, N,N-dioctadecylureido,
N,N-dioctyl-N'-ethylureido, N-phenylureido, N,N-diphenylureido,
N-phenyl-N-p-toluylureido, N-(m-hexadecylphenyl)ureido,
N,N-(2,5-di-t-pentylphenyl)-N'-ethylureido, and t-butylcarbonamido;
sulfonamido, such as methylsulfonamido, benzenesulfonamido,
p-toluylsulfonamido, p-dodecylbenzenesulfonamido,
N-methyltetradecylsulfo- namido, N,N-dipropyl-sulfamoylamino, and
hexadecylsulfonamido; sulfamoyl, such as N-methylsulfamoyl,
N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-hexadecylsulfamoyl,
N,N-dimethylsulfamoyl; N-[3-(dodecyloxy)propyl]sulf- amoyl,
N-[4-(2,4-di-t-pentylphenoxy)butyl]sulfamoyl,
N-methyl-N-tetradecylsulfamoyl, and N-dodecylsulfamoyl; carbamoyl,
such as N-methylcarbamoyl, N,N-dibutylcarbamoyl,
N-octadecylcarbamoyl, N-[4-(2,4-di-t-pentylphenoxy)butyl]carbamoyl,
N-methyl-N-tetradecylcarbam- oyl, and N,N-dioctylcarbamoyl; acyl,
such as acetyl, (2,4-di-t-amylphenoxy)acetyl, phenoxycarbonyl,
p-dodecyloxyphenoxycarbony- l methoxycarbonyl, butoxycarbonyl,
tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl,
3-pentadecyloxycarbonyl, and dodecyloxycarbonyl; sulfonyl, such as
methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl,
2-ethylhexyloxysulfonyl, phenoxysulfonyl,
2,4-di-t-pentylphenoxysulfonyl, methylsulfonyl, octylsulfonyl,
2-ethylhexylsulfonyl, dodecylsulfonyl, hexadecylsulfonyl,
phenylsulfonyl, 4-nonylphenylsulfonyl, and p-toluylsulfonyl;
sulfonyloxy, such as dodecylsulfonyloxy, and hexadecylsulfonyloxy;
sulfinyl, such as methylsulfinyl, octylsulfinyl,
2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl,
phenylsulfinyl, 4-nonylphenylsulfinyl, and p-toluylsulfinyl; thio,
such as ethylthio, octylthio, benzylthio, tetradecylthio,
2-(2,4-di-t-pentylphenoxy)ethylthio, phenylthio,
2-butoxy-5-t-octylphenylthio, and p-tolylthio; acyloxy, such as
acetyloxy, benzoyloxy, octadecanoyloxy, p-dodecylamidobenzoyloxy,
N-phenylcarbamoyloxy, N-ethylcarbamoyloxy, and
cyclohexylcarbonyloxy; amine, such as phenylanilino,
2-chloroanilino, diethylamine, dodecylamine; imino, such as
1(N-phenylimido)ethyl, N-succinimido or 3-benzylhydantoinyl;
phosphate, such as dimethylphosphate and ethylbutylphosphate;
phosphite, such as diethyl and dihexylphosphite; a heterocyclic
group, a heterocyclic oxy group or a heterocyclic thio group, each
of which may be substituted and which contain a 3- to 7-membered
heterocyclic ring composed of carbon atoms and at least one hetero
atom selected from the group consisting of oxygen, nitrogen and
sulfur, such as 2-furyl, 2-thienyl, 2-benzimidazolyloxy or
2-benzothiazolyl, quaternary ammonium, such as triethylammonium;
and silyloxy, such as trimethylsilyloxy.
[0051] If desired, the substituents may themselves be further
substituted one or more times with the described substituent
groups. The particular substituents used may be selected by those
skilled in the art to attain the desired photographic properties
for a specific application and can include, for example,
hydrophobic groups, solubilizing groups, blocking groups, releasing
or releasable groups, etc. Generally, the above groups and
substituents thereof may include those having up to 48 carbon
atoms, typically 1 to 36 carbon atoms and usually less than 24
carbon atoms, but greater numbers are possible depending on the
particular substituents selected.
[0052] The photographic elements utilized in the invention contain
more than one image dye-forming unit. Generally the photographic
elements contain image dye-forming units sensitive to each of the
three primary regions of the spectrum. Each unit can comprise a
single emulsion layer or multiple emulsion layers sensitive to a
given region of the spectrum. It is preferred that each unit
contain multiple emulsion layers. The layers of the element,
including the layers of the image-forming units, can be arranged in
various orders as known in the art. The ETARC utilized in the
invention is contained in the dye image unit closest to the
support. It is preferred that the ETARC utilized in the invention
is contained in the least light sensitive layer of the color unit
closest to the support.
[0053] In one suitable embodiment, the photographic element of this
invention comprises a support bearing, in order from the support, a
cyan dye image-forming unit comprised of at least one red-sensitive
silver halide emulsion layer having associated therewith at least
one cyan dye-forming coupler, a magenta dye image-forming unit
comprising at least one green-sensitive silver halide emulsion
layer having associated therewith at least one magenta dye-forming
coupler, and a yellow dye image-forming unit comprising at least
one blue-sensitive silver halide emulsion layer having associated
therewith at least one yellow dye-forming coupler. The ETARC is
contained in the red-sensitive layer. The element can contain
additional layers, such as filter layers, interlayers, overcoat
layers, subbing layers, and the like.
[0054] If desired, the photographic element can be used in
conjunction with an applied magnetic layer as described in Research
Disclosure, November 1992, Item 34390 published by Kenneth Mason
Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, N.H.
PO10 7DQ, ENGLAND, the contents of which are incorporated herein by
reference. Further, the photographic elements may have an annealed
polyethylene naphthalate film base such as described in Hatsumei
Kyoukai Koukai Gihou No. 94-6023, published Mar. 15, 1994 (Patent
Office of Japan and Library of Congress of Japan) and may be
utilized in a small format system, such as described in Research
Disclosure, June 1994, Item 36230 published by Kenneth Mason
Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, N.H.
PO10 7DQ, ENGLAND, and such as the Advanced Photo System,
particularly the Kodak ADVANTIX films or cameras.
[0055] In the following Table, reference will be made to (1)
Research Disclosure, December 1978, Item 17643; (2) Research
Disclosure, December 1989, Item 308119; (3) Research Disclosure,
September 1994, Item 36544; and (4) Research Disclosure, September
1996, Item 38957, all published by Kenneth Mason Publications,
Ltd., Dudley Annex, 12a North Street, Emsworth, N.H. PO10 7DQ,
ENGLAND, the disclosures of which are incorporated herein by
reference. The Table and the references cited in the Table are to
be read as describing particular components suitable for use in the
elements of the invention. The Table and its cited references also
describe suitable ways of preparing, exposing, processing and
manipulating the elements, and the images contained therein.
Photographic elements and methods of processing such elements
particularly suitable for use with this invention are described in
Research Disclosure, February 1995, Item 37038 and in Research
Disclosure, September 1997, Item 40145 published by Kenneth Mason
Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, N.H.
PO10 7DQ, ENGLAND, the disclosure of which is incorporated herein
by reference.
2 Reference Section Subject Matter 1 I, II Grain composition,
morphology and 2 I, II, IX, X, XI, preparation. Emulsion
preparation XII, XIV, XV including hardeners, coating aids, 3 &
4 I, II, III, IX A & B addenda, etc. 1 III, IV Chemical
sensitization and spectral 2 III, IV sensitization/Desensitization
3 & 4 IV, V 1 V UV dyes, optical brighteners, 2 V luminescent
dyes 3 & 4 VI 1 VI Antifoggants and stabilizers 2 VI 3 & 4
VII 1 VIII Absorbing and scattering materials; 2 VIII, XIII, XVI
Antistatic layers; matting agents 3 & 4 VIII, IX C & D 1
VII Image-couplers and image- 2 VII modifying couplers; Wash-out 3
& 4 X couplers; Dye stabilizers and hue modifiers 1 XVII
Supports 2 XVII 3 & 4 XV 3 & 4 XI Specific layer
arrangements 3 & 4 XII, XIII Negative working emulsions; Direct
positive emulsions 2 XVIII Exposure 3 & 4 XVI 1 XIX, XX
Chemical processing; 2 XIX, XX, XXII Developing agents 3 & 4
XVIII, XIX, XX 3 & 4 XIV Scanning and digital processing
procedures
[0056] The photographic elements can be incorporated into exposure
structures intended for repeated use or exposure structures
intended for limited use, variously referred to as single use
cameras, lens with film, or photosensitive material package
units.
[0057] Image dye forming couplers are present in the photographic
elements. The presence of hydrogen at the coupling site provides a
4-equivalent coupler, and the presence of another coupling-off
group usually provides a 2-equivalent coupler. Representative
classes of such coupling-off groups include, for example, chloro,
alkoxy, aryloxy, heteroxy, sulfonyloxy, acyloxy, acyl,
heterocyclyl, sulfonamido, mercaptotetrazole, benzothiazole,
mercaptopropionic acid, phosphonyloxy, arylthio, and arylazo. These
coupling-off groups are described in the art, for example, in U.S.
Pat. Nos. 2,455,169; 3,227,551; 3,432,521; 3,476,563; 3,617,291;
3,880,661; 4,052,212; and 4,134,766; and in UK. Patents and
published application Nos. 1,466,728; 1,531,927; 1,533,039;
2,006,755 A; and 2,017,704 A, the disclosures of which are
incorporated herein by reference.
[0058] Other image dye-forming couplers may be included in the
element such as those image couplers already described above for
CAR. In one preferred embodiment a dye forming coupler is contained
in the same emulsion layer as the ETARC utilized in this invention.
Couplers that form black dyes upon reaction with oxidized color
developing agent are described in such representative patents as
U.S. Pat. Nos. 1,939,231; 2,181,944; 2,333,106; and 4,126,461;
German OLS No. 2,644,194 and German OLS No. 2,650,764. Typically,
such couplers are resorcinols or m-aminophenols that form black or
neutral products on reaction with oxidized color developing
agent.
[0059] In addition to the foregoing, so-called "universal" or
"washout" couplers may be employed. These couplers do not
contribute to image dye-formation. Thus, for example, a naphthol
having an unsubstituted carbamoyl or one substituted with a low
molecular weight substituent at the 2- or 3-position may be
employed. Couplers of this type are described, for example, in U.S.
Pat. Nos. 5,026,628; 5,151,343; and 5,234,800.
[0060] It may be useful to use a combination of couplers any of
which may contain known ballasts or coupling-off groups such as
those described in U.S. Pat. Nos. 4,301,235; 4,853,319; and
4,351,897. The coupler may contain solubilizing groups such as
described in U.S. Pat. No. 4,482,629. The coupler may also be used
in association with "wrong" colored couplers (e.g., to adjust
levels of interlayer correction) and, in color negative
applications, with masking couplers such as those described in EP
213.490; Japanese Published Application 58-172,647; U.S. Pat. Nos.
2,983,608; 4,070,191; and 4,273,861; German Applications DE
2,706,117 and DE 2,643,965; UK. Patent 1,530,272; and Japanese
Application 58-113935. The masking couplers may be shifted or
blocked, if desired.
[0061] The photographic elements may contain materials that
accelerate or otherwise modify the processing steps, e.g., of
bleaching or fixing to improve the quality of the image. Bleach
accelerator releasing couplers such as those described in EP
193,389; EP 301,477; U.S. Pat. No. 4,163,669; U.S. Pat. No.
4,865,956; and U.S. Pat. No. 4,923,784 may be useful. Also
contemplated is use of the compositions in association with
nucleating agents, development accelerators or their precursors (UK
Patents 2,097,140 and 2,131,188); other electron transfer agents
(U.S. Pat. Nos. 4,859,578 and 4,912,025); antifogging and anti
color-mixing agents such as derivatives of hydroquinones,
aminophenols, amines, gallic acid; catechol; ascorbic acid;
hydrazides; sulfonamidophenols; and non color-forming couplers.
[0062] The invention materials may also be used in combination with
filter dye layers comprising colloidal silver sol or yellow, cyan,
and/or magenta filter dyes, either as oil-in-water dispersions,
latex dispersions or as solid particle dispersions. Additionally,
they may be used with "smearing" couplers (e.g., as described in
U.S. Pat. Nos. 4,366,237; 4,420,556; and 4,543,323; and EP 096
570). Also, the compositions may be blocked or coated in protected
form as described, for example, in Japanese Application 61/258,249
or U.S. Pat. No. 5,019,492.
[0063] The invention materials may further be used in combination
with image-modifying compounds such as "Developer
Inhibitor-Releasing" compounds (DIR's). In one suitable embodiment
a DIR compound is contained in the dye imaging unit closest to the
support. It may be contained in any emulsion layer in the dye
imaging unit; however, it is preferably contained in the same layer
as the ETARC utilized in the invention. DIR's useful in conjunction
with the compositions of the invention are known in the art, and
examples are described in U.S. Pat. Nos. 3,137,578; 3,148,022;
3,148,062; 3,227,554; 3,384,657; 3,379,529; 3,615,506; 3,617,291;
3,620,746; 3,701,783; 3,733,201; 4,049,455; 4,095,984; 4,126,459;
4,149,886; 4,150,228; 4,211,562; 4,248,962; 4,259,437; 4,362,878;
4,409,323; 4,477,563, 4,782,012; 4,962,018; 4,500,634; 4,579,816;
4,607,004; 4,618,571; 4,678,739; 4,746,600; 4,746,601; 4,791,049;
4,857,447; 4,865,959; 4,880,342; 4,886,736; 4,937,179; 4,946,767;
4,948,716; 4,952,485; 4,956,269; 4,959,299; 4,966,835; 4,985,336 as
well as in patent publications GB 1,560,240; GB 2,007,662; GB
2,032,914; GB 2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824;
DE 3,644,416, as well as the following European Patent
Publications: 272,573; 335,319; 336,411; 346,899; 362,870; 365,252;
365,346; 373,382; 376,212; 377,463; 378,236; 384,670; 396,486;
401,612; and 401,613.
[0064] Such compounds are also disclosed in
"Developer-Inhibitor-Releasing (DIR) Couplers for Color
Photography," C. R. Barr, J. R. Thirtle and P. W. Vittum in
Photographic Science and Engineering, Vol. 13, p. 174 (1969),
incorporated herein by reference. Generally, the developer
inhibitor-releasing (DIR) couplers include a coupler moiety and an
inhibitor coupling-off moiety (IN). The inhibitor-releasing
couplers may be of the time-delayed type (DIAR couplers) which also
include a timing moiety or chemical switch which produces a delayed
release of inhibitor. Examples of typical inhibitor moieties are:
oxazoles, thiazoles, diazoles, triazoles, oxadiazoles,
thiadiazoles, oxathiazoles, thiatriazoles, benzotriazoles,
tetrazoles, benzimidazoles, indazoles, isoindazoles,
mercaptotetrazoles, selenotetrazoles, mercaptobenzothiazoles,
selenobenzothiazoles, mercaptobenzoxazoles, selenobenzoxazoles,
mercaptobenzimidazoles, selenobenzimidazoles, benzodiazoles,
mercaptooxazoles, mercaptothiadiazoles, mercaptothiazoles,
mercaptotriazoles, mercaptooxadiazoles, mercaptodiazoles,
mercaptooxathiazoles, telleurotetrazoles or benzisodiazoles. In a
preferred embodiment, the inhibitor moiety or group is selected
from the following formulas: 14
[0065] wherein R.sub.I is selected from the group consisting of
straight- and branched-alkyls of from 1 to about 8 carbon atoms,
benzyl, phenyl, and alkoxy groups and such groups containing none,
one, or more than one such substituent; R.sub.II is selected from
R.sub.I and --SR.sub.I; R.sub.III is a straight- or branched-alkyl
group of from 1 to about 5 carbon atoms, and m is from 1 to 3; and
R.sub.IV is selected from the group consisting of hydrogen,
halogens and alkoxy, phenyl and carbonamido groups, --COOR.sub.V
and --NHCOOR.sub.V wherein R.sub.V is selected from substituted and
unsubstituted alkyl and aryl groups.
[0066] Although it is typical that the coupler moiety included in
the developer inhibitor-releasing coupler forms an image dye
corresponding to the layer in which it is located, it may also form
a different color as one associated with a different film layer. It
may also be useful that the coupler moiety included in the
developer inhibitor-releasing coupler forms colorless products
and/or products that wash out of the photographic material during
processing (so-called "universal" couplers).
[0067] As mentioned, the developer inhibitor-releasing coupler may
include a timing group, which produces the time-delayed release of
the inhibitor group such as groups utilizing the cleavage reaction
of a hemiacetal (U.S. Pat. No. 4,146,396, Japanese Applications
60-249148; 60-249149); groups using an intramolecular nucleophilic
substitution reaction (U.S. Pat. No. 4,248,962); groups utilizing
an electron transfer reaction along a conjugated system (U.S. Pat.
Nos. 4,409,323 and 4,421,845; Japanese Applications 57-188035;
58-98728; 58-209736; and 58-209738) groups utilizing ester
hydrolysis (German Patent Application (OLS) No. 2,626,315); groups
utilizing the cleavage of imino ketals (U.S. Pat. No. 4,546,073);
groups that function as a coupler or reducing agent after the
coupler reaction (U.S. Pat. Nos. 4,438,193 and 4,618,571) and
groups that combine the features describe above. It is typical that
the timing group or moiety is of one of the formulas: 15
[0068] wherein IN is the inhibitor moiety, Z' is selected from the
group consisting of nitro, cyano, alkylsulfonyl; sulfamoyl
(--SO.sub.2NR.sub.2); and sulfonamido (--NRSO.sub.2R) groups; n is
0 or 1; and R.sub.VI is selected from the group consisting of
substituted and unsubstituted alkyl and phenyl groups. The oxygen
atom of each timing group is bonded to the coupling-off position of
the respective coupler moiety of the DIAR.
[0069] Suitable developer inhibitor-releasing couplers for use in
the present invention include, but are not limited to, the
following: 161718
[0070] The silver halide emulsions utilized in this invention are
bromoiodide emulsions. Generally, the iodide content of such silver
bromoiodide emulsions is less than about 40 mol % (based on total
silver), preferably from about 0.05 to about 10 mol %, and more
preferably from about 0. 5 to about 6 mol %. The emulsions can be
of any crystal morphology (such as cubic, octahedral,
cubooctahedral, or tabular as are known in the art), or irregular
morphology (such as multiple twinning or rounded). Especially
useful in this invention are tabular grain silver halide emulsions.
Tabular grains are those having two parallel major crystal faces
and having an aspect ratio of at least 2. The term "aspect ratio"
is the ratio of the equivalent circular diameter (ECD) of a grain
major face divided by its thickness (t). Tabular grain emulsions
are those in which the tabular grains account for at least 50
percent (preferably at least 70 percent and optimally at least 90
percent) of the total grain projected area. Preferred tabular grain
emulsions are those in which the average thickness of the tabular
grains is less than 0.3 micrometer (preferably thin--that is, less
than 0.2 micrometer and most preferably ultrathin--that is, less
than 0.07 micrometer). The major faces of the tabular grains can
lie in either {111} or {100} crystal planes. The mean ECD of
tabular grain emulsions rarely exceeds 10 micrometers and more
typically is less than 5 micrometers.
[0071] In their most widely used form tabular grain emulsions are
high bromide {111} tabular grain emulsions. Such emulsions are
illustrated by Kofron et al U.S. Pat. No. 4,439,520; Wilgus et al
U.S. Pat. No. 4,434,226; Solberg et al U.S. Pat. No. 4,433,048;
Maskasky U.S. Pat. Nos. 4,435,501; 4,463,087; and 4,173,320;
Daubendiek et al U.S. Pat. Nos. 4,414,310 and 4,914,014, Sowinski
et al U.S. Pat. No. 4,656,122; Piggin et al U.S. Pat. Nos.
5,061,616 and 5,061,609, Tsaur et al U.S. Pat. Nos. 5,147,771;
'772; '773; 5,171,659; and 5,252,453; Black et al U.S. Pat. Nos.
5,219,720 and 5,334,495; Delton U.S. Pat. Nos. 5,310,644;
5,372,927; and 5,460,934; Wen U.S. Pat. No. 5,470,698; Fenton et al
U.S. Pat. No. 5,476,760; Eshelman et al U.S. Pat. Nos. 5,612,175
and 5,614,359; and Irving et al U.S. Pat. No. 5,667,954.
[0072] Ultrathin high bromide {111} tabular grain emulsions are
illustrated by Daubendiek et al U.S. Pat. Nos. 4,672,027,
4,693,964; 5,494,789; 5,503,971; and 5,576,168; Antoniades et al
U.S. Pat. No. 5,250,403; Olm et al U.S. Pat. No. 5,503,970; Deaton
et al U.S. Pat. No. 5,582,965; and Maskasky U.S. Pat. No.
5,667,955. High bromide {100} tabular grain emulsions are
illustrated by Mignot U.S. Pat. Nos. 4,386,156 and 5,386,156.
[0073] Such color silver bromoiodide elements generally have a
camera speed defined as an ISO speed of at least 25, preferably an
ISO speed of at least 50, and more preferably an ISO speed of at
least 100. The speed or sensitivity of color negative photographic
materials is inversely related to the exposure required to enable
the attainment of a specified density above fog after processing.
Photographic speed for color negative films with a gamma of about
0.65 has been specifically defined by the American National
Standards Institute (ANSI) as ANSI Standard Number PH 2.27-1979
(ASA speed) and relates to the exposure levels required to enable a
density of 0.15 above fog in the green light sensitive and least
sensitive recording unit of a multicolor negative film. This
definition conforms to the International Standards Organization
(ISO) film speed rating.
[0074] The photographic elements are preferably exposed to actinic
radiation, typically in the visible region of the spectrum, to form
a latent image, and then processed to form a visible dye image.
Development is typically followed by the conventional steps of
bleaching, fixing, or bleach-fixing, to remove silver or silver
halide, washing, and drying.
[0075] In the method of the invention the photographic element is
contacted with the color developer for less than 120 seconds, with
a time of from about 20 to about 120 seconds being preferred. More
preferably, the photographic element is contacted with the color
developer for 100 seconds or less, and most preferably for 60
seconds or less. The overall processing time (from development to
final rinse or wash) can be from about 40 seconds to about 40
minutes. Shorter overall processing times, that is, less than about
3 minutes, are desired for processing photographic color negative
films according to this invention. For rapid color development, the
processing temperature is generally from about 40 to about
65.degree. C., preferably from about 45 to about 65.degree. C., and
more preferably from about 50 to about 60.degree. C. Most
preferably, the development temperature is from about 55 to about
60.degree. C.
[0076] The length of time and temperatures used for each processing
step of the present invention, other than color development, can be
any desired condition, whether conventional or not.
[0077] The color developing compositions used in this invention
include one or more color developing agents that are well known in
the art that, in oxidized form, will react with dye forming color
couplers in the processed materials. Such color developing agents
include, but are not limited to, aminophenols, p-phenylenediamines
(especially N,N-dialkyl-p-phenylenediamines) and others which are
well known in the art, such as EP 0 434 097 A1 (published Jun. 26,
1991) and EP 0 530 921 A1 (published Mar. 10, 1993). It may be
useful for the color developing agents to have one or more
water-solubilizing groups as are known in the art. Further details
of such materials are provided in Research Disclosure, publication
38957, pages 592-639 (September 1996).
[0078] Preferred color developing agents include, but are not
limited to, N,N-diethyl p-phenylenediamine sulfate (KODAK Color
Developing Agent CD-2), 4-amino-3-methyl-N-(2-methane
sulfonamidoethyl)aniline sulfate,
4-(N-ethyl-N-2'-hydroxyethylamino)-2-methylaniline sulfate (KODAK
Color Developing Agent CD-4), p-hydroxyethylethylaminoaniline
sulfate,
4-(N-ethyl-N-2-methanesulfonylaminoethyl)-2-methylphenylenediamine
sesquisulfate (KODAK Color Developing Agent CD-3),
4-(N-ethyl-N-2-methanesulfonylaminoethyl)-2-methylphenylenediamine
sesquisulfate, and others readily apparent to one skilled in the
art. Particularly suitable for use in the current invention is
4-(N-ethyl-N-2'-hydroxyethylamino)-2-methylaniline sulfate (KODAK
Color Developing Agent CD-4).
[0079] In order to protect the color developing agents from
oxidation, one or more antioxidants are generally included in the
color developing compositions. In the developer compositions used
in the invention both a sulfite compound (such as sodium sulfite,
potassium sulfite, sodium bisulfite, and potassium metabisulfite)
and an additional antioxidant are utilized. Either inorganic or
organic antioxidants can be used as the additional antioxidant.
Many classes of useful antioxidants are known, including but not
limited to, hydroxylamine (and derivatives thereof), hydrazines,
hydrazides, amino acids, ascorbic acid (and derivatives thereof),
hydroxamic acids, aminoketones, mono- and polysaccharides, mono-
and polyamines, quaternary ammonium salts, nitroxy radicals,
alcohols, and oximes. Also useful as antioxidants are
1,4-cyclobexadiones as described in U.S. Pat. No. 6,077,653.
Mixtures of compounds from the same or different classes of
antioxidants can also be used if desired.
[0080] The most preferred antioxidant for use in this invention is
hydroxylamine sulfate. Other useful antioxidants are hydroxylamine
derivatives as described, for example, in U.S. Pat. Nos. 4,892,804
(Vincent et al), 4,876,174 (Ishikawa et al), 5,354,646 (Kobayashi
et al), 5,660,974 (Marrese et al), and 5,646,327 (Burns et al), the
disclosures of which are all incorporated herein by reference with
respect to antioxidants. Many of these antioxidants are mono- and
dialkylhydroxylamines having one or more substituents on one or
both alkyl groups. Particularly useful alkyl substituents include
sulfo, carboxy, amino, sulfonamido, carbonamido, hydroxy, and other
solubilizing substituents.
[0081] The noted hydroxylamine derivatives can be mono- or
dialkylhydroxylamines having one or more hydroxy substituents on
the one or more alkyl groups. Representative compounds of this type
are described, for example, in U.S. Pat. No. 5,709,982 (Marrese et
al), incorporated herein by reference, as having the following
Structure I: 19
[0082] wherein R is hydrogen, a substituted or unsubstituted alkyl
group of 1 to 10 carbon atoms, a substituted or unsubstituted
hydroxyalkyl group of 1 to 10 carbon atoms, a substituted or
unsubstituted cycloalkyl group of 5 to 10 carbon atoms, or a
substituted or unsubstituted aryl group having 6 to 10 carbon atoms
in the aromatic nucleus.
[0083] X.sub.1 is --CR.sub.2(OH)CHR.sub.3-- and X.sub.2 is
--CHR.sub.1CR.sub.2(OH)-- wherein R.sub.1 and R.sub.2 are
independently hydrogen, hydroxy, a substituted or unsubstituted
alkyl group or 1 or 2 carbon atoms, a substituted or unsubstituted
hydroxyalkyl group of 1 or 2 carbon atoms, or R.sub.1 and R.sub.2
together represent the carbon atoms necessary to complete a
substituted or unsubstituted 5- to 8-membered saturated or
unsaturated carbocyclic ring structure.
[0084] Y is a substituted or unsubstituted alkylene group having at
least 4 carbon atoms, and has an even number of carbon atoms, or Y
is a substituted or unsubstituted divalent aliphatic group having
an even total number of carbon and oxygen atoms in the chain,
provided that the aliphatic group has a least 4 atoms in the
chain.
[0085] Also in Structure I, m, n and p are independently 0 or 1.
Preferably, each of m and n is 1, and p is 0.
[0086] Specific di-substituted hydroxylamine antioxidants include,
but are not limited to, N,N-bis(2,3-dihydroxypropyl)hydroxylamine,
N,N-bis(2-methyl-2,3-dihydroxypropyl)hydroxylamine and
N,N-bis(1-hydroxymethyl-2-hydroxy-3-phenylpropyl)hydroxylamine. The
first compound is preferred.
[0087] Also useful are the antioxidants disclosed in U.S. Pat. No.
5,827,635 represented by the formula:
R"--L--N(OH)--L'--R'
[0088] wherein L and L' are independently substituted or
unsubstituted alkylene of 1 to 8 carbon atoms (such as methylene,
ethylene, n-propylene, isopropylene, n-butylene,
1,1-dimethylethylene, n-hexylene, n-octylene and sec-butylene), or
substituted or unsubstituted alkylenephenylene of 1 to 3 carbon
atoms in the alkylene portion (such as benzylene,
dimethylenephenylene, and isopropylenephenylene).
[0089] The alkylene and alkylenephenylene groups can also be
substituted with up to 4 substituents that do not interfere with
the stabilizing effect of the molecule, or the solubility of the
compound in the color developer solution. Such substituents must be
compatible with the color developer components and must not
negatively impact the photographic processing system. Such
substituents include, but are not limited to, alkyl of 1 to 6
carbon atoms, fluoroalkyl groups of 1 to 6 carbon atoms, alkoxy of
1 to 6 carbon atoms, phenyl, hydroxy, halo, phenoxy, alkylthio of 1
to 6 carbon atoms, acyl groups, cyano, or amino.
[0090] In the noted formula, R" and R' are independently hydrogen,
carboxy, sulfo, phosphono, or other acid groups, provided that at
least one of R" and R' is not hydrogen. Salts of the acid groups
are considered equivalents in this invention. Thus, the free acid
forms of the hydroxylamines can be used, as well as the organic or
inorganic salts of the acids, such as the alkali metal, pyridinium,
tetraethylammonium, tetramethylammonium and ammonium salts. The
sodium and potassium salts are the preferred salts. In addition,
readily hydrolyzable ester equivalents can also be used, such as
the methyl and ethyl esters of the acids. When L or L' is
alkylenephenylene, the carboxy, sulfo or phosphono group is
preferably at the para position of the phenylene, but can be at
other positions if desired. More than one carboxy, sulfo, or
phosphono group can be attached to the phenylene radical.
[0091] Preferably, one or both of R" and R' are hydrogen, carboxy
or sulfo, with hydrogen and sulfo (or salts or readily hydrolyzable
esters thereof) being more preferred. Most preferably, R is
hydrogen and R' is sulfo (or a salt thereof).
[0092] Preferably, L and L' are independently substituted or
unsubstituted alkylene of 3 to 6 carbon atoms (such as n-propyl,
isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, 1-methylpentyl
and 2-ethylbutyl), or substituted or unsubstituted
alkylenephenylene having 1 or 2 carbon atoms in the alkylene
portion (such as benzyl and dimethylenephenyl).
[0093] More preferably, at least one, and optionally both, of L and
L' is a substituted or unsubstituted alkylene group of 3 to 6
carbon atoms that is branched at the carbon atom directly attached
(that is, covalently bonded) to the nitrogen atom of the
hydroxylamine molecule. Such branched divalent groups include, but
are not limited to, isopropylene, sec-butylene, t-butylene,
sec-pentylene, t-pentylene, sec-hexylene and t-hexylene.
Isopropylene is most preferred.
[0094] In one embodiment, L and L' are the same. In other and
preferred embodiments, they are different. In the latter
embodiment, L is more preferably a branched alkylene as described
above, and L' is a linear alkylene of 1 to 6 carbon atoms (such as
methylene, ethylene, n-propylene, n-butylene, n-pentylene and
n-hexylene).
[0095] Representative hydroxylamine derivatives useful in the
practice of this invention include, but are not limited to,
N-isopropyl-N-(2-ethanesu- lfonic acid)hydroxylamine,
N,N-bis(propionic acid)hydroxylamine, N,N-bis(2-ethanesulfonic
acid)hydroxylamine, N-isopropyl-N-(n-propylsulfo- nic
acid)hydroxylamine, N-2-ethanephosphonic acid-N-(propionic
acid)hydroxylaamine, N,N-bis(2-ethanephosphonic acid)hydroxylamine,
N-sec-butyl-N-(2-ethanesulfonic acid)hydroxylamine,
N,N-bis(sec-butylcarboxylic acid)hydroxylamine,
N-methyl-N-(p-carboxylben- zyl)hydroxylamine,
N-isopropyl-N-(p-carboxylbenzyl)hydroxylamine,
N,N-bis(p-carboxylbenzyl)hydroxylamine,
N-methyl-N-(p-carboxyl-m-methylbe- nzyl)hydroxylamine,
N-isopropyl-N-(p-sulfobenzyl)hydroxylamine,
N-ethyl-N-(p-phosphonobenzyl)hydroxylamine,
N-isopropyl-N-(2-carboxymethy- lene-3-propionic acid)hydroxylamine,
and alkali metal salts thereof.
[0096] Many of the noted antioxidants (organic or inorganic) are
either commercially available or prepared using starting materials
and procedures described in the references noted above in
describing hydroxylamines.
[0097] Buffering agents are generally present in the color
developing compositions used in this invention to provide or
maintain the desired alkaline pH of from about 9 to about 12, and
more preferably from about 9 to about 11. These buffering agents
must be soluble in the organic solvent described herein and have a
pKa of from about 9 to about 13. Such useful buffering agents
include, but are not limited to, carbonates, borates, tetraborates,
glycine salts, triethanolamine, diethanolamine, phosphates, and
hydroxybenzoates. Alkali metal carbonates (such as sodium
carbonate, sodium bicarbonate, and potassium carbonate) are
preferred buffering agents. Mixtures of buffering agents can be
used if desired.
[0098] In addition to buffering agents, pH can also be raised or
lowered to a desired value using one or more acids or bases. It may
be particularly desirable to raise the pH by adding a base, such as
a hydroxide (for example, sodium hydroxide or potassium
hydroxide).
[0099] An optional but preferred component of the color developing
compositions used in this invention is a photographically inactive,
water-miscible or water-soluble, straight-chain organic solvent,
that is, capable of dissolving color developing agents in their
free base forms. Such organic solvents can be used singly or in
combination, and preferably each has a molecular weight of at least
50, and preferably at least 100, and generally 200 or less, and
preferably 150 or less. Such preferred solvents generally have from
2 to 10 carbon atoms (preferably from 2 to 6 carbon atoms, and more
preferably from 4 to 6 carbon atoms), and can additionally contain
at least two nitrogen or oxygen atoms, or at least one of each
heteroatom. The organic solvents are substituted with at least one
hydroxy functional group, and preferably at least two of such
groups. They are straight-chain molecules, not cyclic
molecules.
[0100] By "photographically inactive" is meant that the organic
solvents provide no substantial positive or negative effect upon
the color developing function of the concentrate.
[0101] Useful organic solvents include, but are not limited to,
polyols including glycols (such as ethylene glycol, diethylene
glycol and triethylene glycol), polyhydroxyamines (including
polyalcoholamines), and alcohols (such as ethanol and benzyl
alcohol). Glycols are preferred with ethylene glycol, diethylene
glycol and triethylene glycol being most preferred. Of the
alcohols, ethanol and benzyl alcohol are most preferred. The most
preferred organic solvent is diethylene glycol.
[0102] The solution can also include one or more of a variety of
other addenda which are commonly used in such compositions, such as
alkali metal halides (such as potassium chloride, potassium
bromide, sodium bromide, and sodium iodide), metal sequestering
agents (such as polycarboxylic or aminopolycarboxylic acids or
polyphosphonates), buffers (as noted above), other preservatives
(such as sulfites and alcoholamines), antifoggants, development
accelerators, optical brighteners, wetting agents, stain reducing
agents, surfactants, defoaming agents, and water-soluble or
water-dispersible color couplers, as would be readily understood by
one skilled in the art (see, for example, Research Disclosure,
noted above and U.S. Pat. No. 4,814,260 of Koboshi et al). The
amounts of such additives are well known in the art also. For
example, the amounts of halides can be varied widely, but are
generally at least about 5.times.10.sup.-5 to about 0.4 mol/l for
bromide ion and at least about 5.times.10.sup.-7 and up to about
0.01 mol/l for iodide ion. The color developing solution may or may
not contain chloride ion because chloride ion essentially has no
effect on the efficacy of the color developer composition. Thus,
generally, chloride ion is not added or present, but if it is, it
is not detrimental to the invention. It is more important that some
bromide and iodide ions be present in the color developer solution.
Other anions besides bromide or iodide may also be utilized, for
example, thiocyanate, that is used in the black-and-white developer
for Ektachrome E-6 processing. The ability to put more Ag+ into
solution is also advantageous for development, and typically is
called solution physical development. Anions that form silver salts
with Ksp values greater than the Ksp value for AgBr, such as NH3,
Ag ligands, and both linear and cyclic polyethers and
polythioethers, would promote solution physical development.
[0103] It is preferred, but not required, that no lithium or
magnesium ions are purposely added to the color developing
compositions used in this invention. Depending upon the
concentrations of such ions in water used to make up processing
solutions, or carried over from previous processing baths, the
total concentration (that is, the sum) of these ions remains
preferably very low, that is less than 0.0001 mol/l in the
compositions, and preferably a total of less than 0.00001
mol/l.
[0104] Exemplary color developing compositions and components are
described, for example, in U.S. application Ser. No. 09/706,006 of
Arcus et al, U.S. application Ser. No. 09/706,463 of Haye et al,
and U.S. application Ser. No. 09/706,474 of Arcus et al, all filed
Nov. 3, 2000, all incorporated herein for their teaching about
color developing compositions.
[0105] The color developing composition is preferably formulated
and used as an aqueous solution, either as the working developer
solution or as a replenishing solution. They can be added to the
processors as single-part solutions or multi-part solutions. They
can also be formulated as gels, powders, and crystalline
suspensions. They can also be formulated and used as dry tablets.
The technology for this is readily known in the art, such as U.S.
Pat. Nos. 5,362,610 (Yoshimoto), 5,376,509 (Yoshimoto et al), and
EP 0 611 986 A1 (published Aug. 24, 1994).
[0106] Processing according to the present invention can be carried
out using conventional deep tanks holding processing solutions or
automatic processing machines. Alternatively, it can be carried out
using what is known in the art as "low volume thin tank" processing
systems, or LVTT, which have either a rack and tank or automatic
tray design. Such processing methods and equipment are described,
for example, in U.S. Pat. No. 5,436,118 (Carli et al) and
publications noted therein. Processing can also be carried out in
minilabs.
[0107] Processing according to the present invention can be carried
out using less conventional processors such as those described in
U. S. Pat. Nos. 5,864,729; 5,890,028; or 5,960,227; a drum
processor such as the Kodak RS-11 Drum Processor, or the wave
processor described in U.S. application Ser. No. 09/920,495, filed
Aug. 1, 2001, the disclosure of which is incorporated herein by
reference. This is a small processor that uses small volumes of
processing solutions once to process photographic material. It
processes the material with only a few millilitres of processing
solution which is then collected as waste. This processor processes
a photographic material by loading the material into a chamber,
introducing a metered amount of processing solution into the
chamber, and rotating the chamber in a fashion which forms a wave
in the solution through which the material passes, the whole volume
of solution for a given stage being spread over the whole material
area in a repetitive manner to enable uniform processing.. The
appropriate solution for each processing stage is added and removed
sequentially from the processing space.
[0108] Another processor and processing method with which the
current invention is particularly useful is the merged process
described in U.S. application Ser. No. ______ of Twist, "Processing
Photographic Material" filed on Oct. 30, 2001, the disclosure of
which is incorporated herein by reference. This processing method
for silver halide photographic material comprises loading the
material into a chamber, introducing a metered amount of a first
processing solution into the chamber, and processing the
photographic material with the first processing solution. It then
comprises introducing a metered amount of a second processing
solution into the chamber without removing the first processing
solution so that at least part of the whole volume of the second
processing solution is provided by the first processing solution
and processing the photographic material with the second processing
solution. The merged method further comprises, after processing the
photographic material with the second processing solution,
introducing a metered amount of a third processing solution into
the chamber without removing any processing solution remaining from
the preceding processing solution or solutions so that at least
part of the total volume of the third processing solution is
provided by the preceding processing solution or solutions and
processing the photographic material with the third processing
solution.
[0109] Besides the component chemistry of the developer, the
agitation and the mode of contact of the developer to the film can
change the rapidity of development. Typically, the more agitation,
the greater is the development speed more developer gets into the
film and more development by-products (typically development
inhibitors such as bromide, iodide), are removed from the film.
Film agitation can involve one or more of the following: film
movement through the developer, gas bubbles, mechanical agitation,
pumping, rollers, wipers, ultrasonics, pads, rollers, dip and dunk,
etc. The developer solutions can be replenished as in a minilab or
deeptank processor, or can be single use, such as the
above-described rotating chamber and the small, hand-held Nicor
reels and tanks.
[0110] The silver bromoiodide elements of the invention are
generally sold packaged with instructions to process in known color
negative processes such as the Kodak C-41 process as described in
The British Journal of Photography Annual of 1988, pages 191-198.
If a color negative film element is to be subsequently employed to
generate a viewable projection print as for a motion picture, a
process such as the Kodak ECN-2 process described in the H-24
Manual available from Eastman Kodak Co. may be employed to provide
the color negative image on a transparent support.
[0111] The following examples are intended to illustrate, but not
to limit the invention.
EXAMPLES
Example 1
[0112] Preparation of Film Samples
[0113] Sample 1: A multilayer photographic element was prepared by
forming the following layers on a cellulose triacetate film
support:
3 Layer 1: Antihalation Layer Black colloid silver 0.15 g/m.sup.2
as silver Gelatin 1.61 g/m.sup.2 OxDS-1 0.081 This layer also
includes absorber dyes to ensure speed matches between layer
responses. Layer 2: First Red Sensitive Emulsion Layer Silver
Bromoiodide emulsion 0.65 g/m.sup.2 (1.5% iodide, mean grain size
0.55 .times. 0.083 .mu.m) Silver Bromoiodide emulsion 0.48 (4.1%
iodide, mean grain size 0.66 .times. 0.12 .mu.m) Coupler CC-1 0.55
Coupler BA-1 0.086 Coupler CD-1 0.034 Gelatin 0.79 Layer 3: Second
Red Sensitive Emulsion Layer Silver Bromoiodide emulsion 0.34
g/m.sup.2 (4.1% iodide, mean grain size 1.22 .times. 0.11 .mu.m)
Silver Bromoiodide emulsion 0.43 (4.1% iodide, mean grain size 1.07
.times. 0.114 .mu.m) Coupler CC-1 0.27 Coupler CD-2 0.038 Coupler
CM-1 0.016 Gelatin 1.130 Layer 4: Third Red Sensitive Emulsion
Layer Silver Bromoiodide emulsion 0.86 g/m.sup.2 (0/3.7% iodide,
mean grain size 1.42 .times. 0.132 .mu.m) Coupler CD-3 0.043
Coupler CD-1 0.059 Coupler CM-1 0.038 Coupler CC-1 0.102 Coupler
CC-2 0.033 Gelatin 1.635 Layer 5: Interlayer Gelatin 0.54 g/m.sup.2
OxDS-1 0.081 Layer 6: First Green Sensitive Emulsion Layer Silver
Bromoiodide emulsion 0.17 g/m.sup.2 (0/4.5% iodide, mean grain size
0.57 .times. 0.111 .mu.m) Silver Bromoiodide emulsion 0.29 (3.5%
iodide, mean grain size 0.28 .mu.m cube) Silver Bromoiodide
emulsion 0.29 (0/3% iodide, mean grain size 0.46 .times. 0.114
.mu.m) Coupler MC-1 0.43 Coupler MM-1 0.11 Coupler MD-1 0.031
Gelatin 1.52 Layer 7: Second Green Sensitive Emulsion Layer Silver
Bromoiodide emulsion 0.71 g/m.sup.2 (0/4.5% iodide, mean grain size
0.75 .times. 0.126 .mu.m) Silver Bromoiodide emulsion 0.15 (0/3%
iodide, mean grain size 0.46 .times. 0.114 .mu.m) Coupler MC-1 0.25
Coupler MM-1 0.12 Coupler MD-1 0.024 Coupler MD-2 0.027 Gelatin
1.45 Layer 8: Third Green Sensitive Emulsion Layer Silver
Bromoiodide emulsion 0.77 g/m.sup.2 (0/4.5% iodide, mean grain size
1.19 .times. 0.128 .mu.m) Coupler MC-1 0.11 Coupler MM-1 0.03
Coupler MD-2 0.036 Coupler MD-3 0.003 Gelatin 0.94 Layer 9: Yellow
Filter Layer Gelatin 0.54 g/m.sup.2 OxDS-1 0.075 Dye YFD-1 0.10
BI-1 0.043 Layer 10: First Blue Sensitive Emulsion Layer Silver
Bromoiodide emulsion 0.18 g/m.sup.2 (1.5% iodide, mean grain size
0.55 .times. 0.083 .mu.m) Silver Bromoiodide emulsion 0.36 (1.5%
iodide, mean grain size 0.77 .times. 0.14 .mu.m) Silver Bromoiodide
emulsion 0.32 (4.1% iodide, mean grain size 1.25 .times. 0.137
.mu.m) Coupler YC-1 0.70 Coupler YC-2 0.43 Coupler YD-1 0.16
Coupler CD-2 0.022 Coupler BA-1 0.005 Gelatin 2.23 Layer 11: Second
Blue Sensitive Emulsion Layer Silver Bromoiodide emulsion 0.31
g/m.sup.2 (4.1% iodide, mean grain size 1.25 .times. 0.137 .mu.m)
Silver Bromoiodide emulsion 0.31 (4.1% iodide, mean grain size 2.67
.times. 0.128 .mu.m) Coupler YC-1 0.26 Coupler YD-1 0.13 Coupler
BA-1 0.005 Gelatin 2.22 Layer 12: First Protective Layer Gelatin
0.70 g/m.sup.2 Silver Bromide Lippmann emulsion 0.22 Dye UV-1 0.10
Dye UV-2 0.10 Layer 13: Second Protective Layer Gelatin 0.89
g/m.sup.2
[0114] Sample 2--as above except the concentration of CC-1 in Layer
3 was reduced to 0.10 mg/m.sup.2 and ETARC compound C-1 was added
to Layer 3 at 0.08 mg/m.sup.2.
[0115] Sample 3--as Sample 2 except the concentration of CC-1 in
Layer 2 was reduced to 0. 38 mg/m.sup.2 and ETARC compound C-1 was
added to Layer 2 at 0.08 mg/m.sup.2.
[0116] Sample 4--as Sample 3 except CC-2 was removed from Layer 4
and ETARC compound C-1 was added to Layer 4 at 0.06 mg/m.sup.2.
[0117] Sample 5--as Sample 1 except the concentration of CC-1 in
Layer 2 was reduced to 0.38 mg/m.sup.2 and ETARC compound C-1 was
added to Layer 2 at 0.08 mg/m.sup.2.
[0118] Sample 6--as Sample 1 except CC-2 was removed from Layer 4
and ETARC compound C-1 was added to Layer 4 at 0.06 mg/m.sup.2.
[0119] Sample 7--as Sample 6 except CC-1 was removed from Layer 4
and the concentration of ETARC compound C-1 in Layer 4 was
increased to 0.075 mg/m.sup.2.
[0120] Sample 8--as Sample 1 except CC-2 was removed from Layer 4
and the concentration of CC-1 in Layer 4 was increased to 0.21
mg/m.sup.2.
[0121] Sample 9--as Sample 8 except DA-1 was added to Layer 5 at
0.043 mg/m.sup.2. 2021222324
Example 2
[0122] The above samples were processed in a Konica rapid process
which is commercially available under the name QD-21 Plus Digital
Minilab, film process cycle "ECOJET HQA-N." and in the Kodak C-41
RA Process (See Example 3 for processing compositions).
4TABLE 1 Comparison of Process C-41 and Process QD-21 Solution Time
(Process QD-21) Time (Process C-41 RA) Developer 1:40 3:15 Bleach
0:24 0:45 Fixer 0:47 1:30 Stabilizer 0:47 1:00
[0123] For each sample, the Lower Scale Contrast (LSC) of the red
curve was measured from the point 0.15 in Status M density above
the minimum density to a point with 0.4 Log H more exposure. The
Mid Scale Contrast (MSC) of the red curve was measured from the
point 0.4 Log H to 1.1 Log H more exposure from the point 0.15 in
Status M density above the minimum density. The Status M density
(above the minimum density) of the red record at 1.8 Log H from the
point 0.15 in density above the minimum density was also measured
(Over exposure density (OD)). Table 2 shows the above parameters
for the samples processed in the QD-21 process. The numbers are
calculated with respect to Sample 1.
5TABLE 2 % Change % Change % Change Sample Layer w/ETARC in LSC in
MSC in OD 1 Comparative example -- -- -- 2 Layer 3 15.2 22.3 8.0 3
Layer 2 + 3 15.0 27.7 13.0 4 Layer 2 + 3 + 4 35.0 17.8 10.5 5 Layer
2 6.1 5.7 10.3 6 Layer 4 10.4 5.7 2.1
[0124] Comparison of Sample 6 to Sample 1 and Sample 4 to Sample 3
demonstrates that the primary effect of adding the ETARC to Layer 4
is a change in contrast in the lower scale. Similarly, comparison
of Sample 3 to Sample 2 and Sample 5 to Sample 1 demonstrates that
the primary effect of adding the ETARC to Layer 2 is a change in
increase in OD, and a smaller effect in LSC than adding the ETARC
to Layer 4. Comparison of Sample 2 to Sample 1 and Sample 2 to
Samples 5 and 6 demonstrates that the MSC is changed more and the
LSC and OD changed less by adding the ETARC to Layer 3 than Layer 2
or 4. Thus, by controlling the level and placement of the ETARC in
a specific layer, the LSC, MSC, and OD of the red sensitive layers
in the rapid process can be selectively adjusted to be more similar
to the green and-blue sensitive layers.
[0125] Table 3 shows the change in MSC and OD for the various
samples in the QD-21 process when compared to the standard C-41
process. The numbers are calculated with respect to each sample in
the C-41 process.
6TABLE 3 % Change % Change Sample Layer w/ETARC in MSC in OD 1
Comparative example -15.2 -16.4 2 Layer 3 -9.4 -12.0 3 Layer 2 + 3
-11.6 -11.8 4 Layer 2 + 3 + 4 -10.0 -8.8 5 Layer 2 -15.7 -15.2 6
Layer 4 -11.6 -14.3
[0126] The above table shows that the loss of contrast and OD in
the rapid access QD-21 process compared to the C-41 process can
also be lessened by proper placement of the ETARC.
Example 3
[0127] Some of the above film samples were processed as follows in
two different rapid process developers and in a comparative
process, the KODAK C-41 Process. The KODAK C-41 Rapid Access
Process steps of bleaching through final rinse were used for all
three processes.
7TABLE 4 Dev. Type RP Dev H RP Dev N C-41 Time (sec) (60) (60)
(195) pH 10.1 10.42 10.07 Temp 48.degree. C. 44.6.degree. C. 37.78
C. MW gm/l gm/l gm/l HAS Hydroxylamine sulfate 164.14 3.0 3.0 3.0
Antical-8 Diethylenetriamine 503.26 2.6 2.6 2.6 pentaacetic acid,
sodium salt KI Potassium iodide 166 0.004 0.004 0.0012 PVP(mer)
Poly(vinyl pyrrolidone) 111.14 3.0 3.0 none NaBr Sodium bromide
102.9 none none 1.3 KBr Potassium bromide 119.01 2 2 none
K.sub.2CO.sub.3 Potassium carbonate 138.21 40 40 37.5 CD-4
4-(N-ethyl-N-2-hydroxy- 292.35 14.0 17.15 4.5
ethyl)-2-methylphenylene- diamine sulfate K.sub.2CO.sub.3 Potassium
sulfite 158 9.0 10.0 none Na.sub.2SO.sub.3 Sodium sulfite 126.04
none none 4.0 Rapid Process (RP) Step Time* Agitation Rapid process
developer 55 + 5 Nitrogen burst, 2 sec. on, 4 sec. Off Kodak C-41
RA bleach 40 + 5 Continuous air bubbles Wash 25 + 5 Continuous air
bubbles Kodak C-41 RA fixer 85 + 5 Continuous air bubbles Wash 25 +
5 Continuous air bubbles Kodak photoflo rinse 55 + 5 None
*Development time is 55 seconds in the sinkline tank and a 5 second
drain and hold above the tank, before dropping the film racks into
the next tank on the sheet).
[0128]
8 Constituent Concentration Chemical Composition of C-41RA bleach,
prepared from replenisher (6.6 L solution 5940A1, diluted to 8 L
and pH adjusted). PDTA (306.277) 0.3709 M = 113.60 g/L Anti-cal 3
(2-OH-PDTA) 2.96 mM = 0.953 g/L Glacial acetic acid 0.8576 M =
51.49 g/L Ammonium bromide 0.967 M = 94.67 g/L Ferric nitrate
nonahydrate 0.3389 M = 136.93 g/L Ammonium hydroxide to pH 4.50
Chemical composition of C-41RA fixer, prepared from concentrate
(4.0 L solution 5784A0, diluted to 8 L and pH adjusted. Ammonium
triosulfate (148.20) 0.7615 M = 112.85 g/L Ammonium sulfite
(116.14) 68.79 mM = 7.990 g/L Sodium sulfite (126.04) 0.1111 M = 14
g/L Ammonium thiocyanate (76.12) 1.182 M = 90 g/L
Na.sub.2EDTA..sub.2H.sub.2O 3.24 mM = 1.2 g Glacial acetic acid
12.82 mM = 0.77 g/L Ammonium hydroxide or sulfuric acid to pH
6.20
[0129] The changes in LSC, MSC, and OD for the two rapid process
developers are given in Table 5. The numbers are calculated with
respect to Sample 1.
9TABLE 5 % Change % Change % Change Sample Layer w/ETARC in LSC in
MSC in OD RP Dev H 1 Comparative example -- -- -- 4 Layer 2 + 3 + 4
33.4 17.1 11.1 6 Layer 4 16.9 2.4 0.4 RP Dev N 1 Comparative
example -- -- -- 4 FC + MC + SC 34.3 18.2 15.0 6 FC 11.3 2.9
3.1
[0130] Comparison on Samples 4 and 6 demonstrate that the placement
of the ETARC effects different parts of the curve.
[0131] Table 6 shows the change in MSC and OD for the various
samples in the two rapid access processes when compared to the
standard C-41 process. The numbers are calculated with respect to
each sample in the C-41 process.
10 TABLE 6 % Change % Change Sample Layer w/ETARC in MSC in OD RP
Dev H 1 Comparative example 14.7 18.1 4 Layer 2 + 3 + 4 10.0 10.1 6
Layer 4 13.9 17.4 RP Dev N 1 Comparative example 24.6 26.4 4 FC +
MC + SC 19.6 16.4 6 FC 23.5 23.7
[0132] The above table shows that the loss of contrast and OD in
the rapid access processes compared to the C-41 process can also be
lessened by proper placement of the ETARC.
[0133] The invention has been described in detail with particular
reference to the preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the scope of the invention.
* * * * *